Manufacture of azo-dyestuffs containing sulphur



' 10 this dyestuff is insufficiently soluble in a. solu- 15 the aforesaid tetrazotized amine with other azo- Patented Sept. 11, 1934 1,973,635-

UNITED STATES PATENT OFFICE MANUFACTURE OF AZO-DYESTUFFS CONTAINING SULPHUR Robert Lantz, Paris, France, assignor of one-half to Societe Anonyme Des Matieres Colorantes & gro'duits Chimiques de Saint-Denis, Paris,

rance No Drawing. Application June 11, 1931, Serial No. 543,746. In France June 19, 1930 13 Claims. (01. 260- 77 Miiller (Zeitschrift fiir Farben-Industrie vol. Ex mp 1 1906 307) has described a dyeswfi made 12.4 parts of para-dithioaniline, which may be by f i tetrazopzed prepared, for examp1e,as described by Louchart d1'amm-oqlpheny1dmu1ph1de) whose 5 (Joum.fiir prakt. Chemie-vol. 41, new series, 1890,

tum mmula p. 200), are dissolved mes parts of hydrochloric 6";

NH NH acid of 22 B. and 300 parts of water. To the r- 2 solution so obtained there are added at ordinary tern erature '70 arts of a solution of sodium ni- Wlth p'naphthyla'nnne; he has mdlcatedthat trite of 10 percent. strength until the nitrite is in slight excess. The whole is then introduced sodutm Sulphlde and therefore wlth' into a solution prepared by dissolving 14.4 parts out interest 1n dyeing in sodium sulphide baths. of flmaphthol whose Structural formula This invention is based on the observation that 7 I the dyestufis, which are obtained by coupling components, have for the most part a good solubility in sodium sulphide solutions and are capable of dyeing in sodium sulphide baths. 1 In particular it is surprising that the dyestufi from 21) a-naphthylamine whose structural formula is: iIi 112 Parts Of a; (iallstic Soda 501111311611 0f NHI and 500 parts'of water. The dyestuii separates immediately in the form of a vivid red precipitate,

which is removed. by filtration and dried. Other dyestuffs maybe obtained in an analo- I 25 5 gous manner if there is used instead of p-naphthol 0 U an equimolecular quantity of e-naphthol whose which is isomeric with that described by Miiller structural formula (10c. cit.) has a good solubility in sodium sul- OH phide solution. I e 0 There may be used as the azo-component a body which-itself contains a. disulphide group, such as bis-(2 hydroxy-naphthyl 6)-disulphide whose structural formula is:

35 6 OH methylphenylpyrazolone whose structural for- V mula is:

. s-s CHr-T=N\' (Zincke et Dereser Ber. d. (1. Chem. Ges., vol. 51, o 1918, p. 357) or the dithioanilide of p-hydroxynaphthoic acid whose structural formula is:

on on CONHQS-SONHCO I h (obtainable in the manner hereinafter de- 2,7-dihydroxynaphthalene whose structural forscribed), or a body containing a trisulphide mula is: v 50 group, such as the trisulphide of a-naphthol whose structural formula is not known obtain- HO OH able as described by Watson and Dutt (Journ. Chem. Soc. vol. 121, p. 2418-9).

The following examples illustrate the invenr V 55 tion, the parts being by weight: 1 01' the like.

acid is destroyed by the addition of a smallquantity of a solution of dithioaniline in hydrochloric acid. The tetrazo solution is then introduced into an aqueous solution of the sulphate of metaphenylenediamine whose structural formula. is: 5

corresponding with 10.8 parts of the base, whereupon the dyestuff separates. 109, parts of. a solu-' tion of sodium acetate of per cent. strength are" added, the whole is allowed to stand for several ed a c mp nent t molecme of which hours and the dyestuff is then separated by filtration. When dry it is a blackpowder having the properties hereinafter described. 7 Y

Tetrazotized dithioaniline may be coupled with a-naphthylamine inlike manner.

Emm e V uble in sodium sulphide solution.

cis

p-hydroxynaphthoic acid dithioanilide may be made in the following mannerz A suspension of 7 parts of ,c-ihydroxynaphthoic acid and 5 parts of QA dithioaniline in anhydrous toluene is heated to -'70 C. 3 parts of phosphorus 'trichloride are then added in small quantities, carebeingtaken' to stir the reaction mixture; whereupon the whole'is heated t'o boiling whilst stirring is continued. When hydrogen chloride is no longer evolved thj whole is rendered alkaline by the addition of sodium car-. bonate and the toluene is removed by distillation with steam. On acidification-p-hydfoxynaph thoic acid dithioanilide is precipitated. It is sparingly soluble in alcohol and boiling acetic acid but is soluble in caustic soda solution and in sodium carbonate solution at a raised temperature. 5

Tetrazotized dithioaniline may be coupled with bis-(2 hydroxynaphthyl 6) disulphide and with the trisulphide of m-naphthol in a manner-analogous to that described in Example 1.

The properties of a number of dyestuffs which can be made in accordance with the invention are indicated in the following table:

azo-component with the exception of B-naphtylamine.

2. A process of manufacturing azo-dyestuffs which comprises coupling tetrazotized 4,4-diaminodiphenyl-disulphide with an unsulphonated azo component containing an amino group, with the exception of B-naphtylamine.

' "3. A process of manufacturing azo-dyestuffs which comprises coupling tetrazotized 4,4'-di- 'flaminodiphenyl-disulphide with metaphenyledi- 'amin' 'e."

L-A process of manufacturing azo-dyestuffs which comprises coupling tetrazotized 4,4-diaminodiphenyl-disulphide with an unsulphonated azo component containing a hydroxy group.

aminodiphenyl-disulphide with an unsulphonatprisesat least one group Sn, n being an integer greater thanl' and smaller than 4.

6.'A process of manufacturing azo-dyestuffs which comprises coupling tetrazotized 4,4'- diaminodiphenyl-disulphidewith an 'unsulphonat ed azo-component the molecule of which comprises the group S2.

'7. A process of manufacturing azo-dyestuffs which comprises coupling tetrazotized 4,4'-diaminodiphenyl-disulphide with B-hydroxynaphthoic acid' dithioanilide. 8. A process of manufacturing azo-dyestuffs which comprises diazotizing para-dithioaniline, introducing the resulting product in a caustic soda solution containing methylphenylpyrazolone, removing byfiltration the dyestuff which precipitates and drying said dyestuff.

A processof manufacturing azo-dyestuffs whichcomprises heating a suspension of 7 parts of B hydroxyn'aphthoic acidrand'5 parts of: 4,4- dithioaniline in anhydrous toluene to 6070 C., adding three parts of phosphorus trichlorid, rendering the whole alkaline when hydrogen chloride is no longer evolved by the addition of sodium carbonate, removing toluene by distillation with steam, acidifying so as to cause .B-hydroxynaphthoic acid dithioanilide to. separate by precipitation and coupling the last men:- tioned compoundwith tetrazotized 4,4'-diaminodiphenyldisulphide.

s a new compound a dyestufl resulting frornthe coupling of tetrazotized dithioaniline with two molecular proportions of methylp'henylpyrazolone, having a yellow-orange color in the dry state and soluble in dilute sodium sulphide solutions and sulphuric acid solutions so as to give yellow and redsolutions, respectively.

11. As a new compound; a dyestuff having a blackcolor in thedry state and soluble in sodium Tetrazotized dithioaniline coupled with 2 gtiglllezceglar proportions of the following sub- Color of the dry powder I gggf g gg gg z 5 2 1 5 Color of gg m Sulphur:

Methylphenylpyrazolone Yellow-orange.- Red. g-naplliltglol Black. glule-rurple.

-nap 10 e 2 7-dihydroxynaphthalene V1oletred a-naphthylamine Blue-purple Bluish-violet. Violet. Orange-brown.. Violet-blue Red-purple What I claim is: 1

1. A process of manufacturing azo-dyestuffs which comprises coupling tetrazotized Adj-diaminodiphenyl-disulfide with an unsulphoriated sulphide and sulphuric Sparingly soluble blue-black.

13. As a. new compound, an azo-dyestufi consisting of the coupling product of tetrazotized 4,4-diaminodiphenyldisulphide with an unsulphonated azo-component with the exception 0: B-naphthylamine, this dyestuff being soluble in sodium sulphide and sulphuric acid solutions.

ROBERT LAN'I'Z. 

